CN110004488A - A kind of graphene/Mn5Ge3/ germanium (110) hetero-junctions and preparation method thereof - Google Patents

A kind of graphene/Mn5Ge3/ germanium (110) hetero-junctions and preparation method thereof Download PDF

Info

Publication number
CN110004488A
CN110004488A CN201910329382.5A CN201910329382A CN110004488A CN 110004488 A CN110004488 A CN 110004488A CN 201910329382 A CN201910329382 A CN 201910329382A CN 110004488 A CN110004488 A CN 110004488A
Authority
CN
China
Prior art keywords
germanium
graphene
sample
preparation
layer graphene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910329382.5A
Other languages
Chinese (zh)
Other versions
CN110004488B (en
Inventor
李昂
崔奋为
朱海龙
黄本锐
马妮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Microsystem and Information Technology of CAS
University of Chinese Academy of Sciences
Original Assignee
Shanghai Institute of Microsystem and Information Technology of CAS
University of Chinese Academy of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Microsystem and Information Technology of CAS, University of Chinese Academy of Sciences filed Critical Shanghai Institute of Microsystem and Information Technology of CAS
Priority to CN201910329382.5A priority Critical patent/CN110004488B/en
Publication of CN110004488A publication Critical patent/CN110004488A/en
Application granted granted Critical
Publication of CN110004488B publication Critical patent/CN110004488B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02373—Group 14 semiconducting materials
    • H01L21/02381—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02441—Group 14 semiconducting materials
    • H01L21/02444—Carbon, e.g. diamond-like carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials

Abstract

The present invention provides a kind of graphene/Mn5Ge3/ germanium (110) hetero-junctions and preparation method thereof, the preparation method is the following steps are included: S1: providing a kind of single-layer graphene sample, coverage rate of the single-layer graphene on germanium (110) substrate is 30%~70%；S2: single-layer graphene sample being put into sample preparation vacuum chamber and is heated, and vacuum degree is 5 × 10‑10~1.5 × 10‑9Millibar, heating temperature are 1050~1150K；S3: changing into 600~650K for the heating temperature of single-layer graphene sample, using evaporation source on single-layer graphene sample hydatogenesis manganese metal；And S4: close evaporation source, keep heating temperature it is constant continue heating to get.The preparation method has many advantages, such as that technical process is simple, and controllability is good, the graphene/Mn5Ge3/ germanium (110) hetero-junctions can be prepared into semiconductor devices because graphene electronic state is in characteristic of semiconductor.

Description

A kind of graphene/Mn5Ge3/ germanium (110) hetero-junctions and preparation method thereof
Technical field
The present invention relates to relate more specifically to a kind of graphene/Mn5Ge3/ germanium (110) hetero-junctions and preparation method thereof.
Background technique
Graphene is a kind of mono-layer graphite, i.e., each carbon atom planar forms two-dimentional six sides in a manner of sp2 hydridization Lattice structure.Graphene has excellent optics, electricity, mechanics, the performances such as material processing, because it is higher than ten times of silicon of carrier Mobility and room temperature half-integer quantum hall effect is shown under externally-applied magnetic field, be generally considered to become next with substituted for silicon For the potentiality of semiconductor material.
Generally existing two drawbacks of the single crystal graphene being prepared out at present, limit its answering in semiconductor field With.First is that graphene is zero gap semiconductor, does not have intrinsic energy gap, cannot be used to do semiconductor devices.Second is that existing Single crystal graphene needs its two-dimensional structure of substrate supports, and the coupling of graphene and substrate can change the electrical property of graphene Can, so that the actual performance of graphene is differed greatly with theoretical performance.
Intercalation is a kind of ideal single crystal graphene modified method, it can not only modulate the electronic state of graphene but also can protect The two-dimentional hexagoinal lattice of card graphene is not destroyed completely.Many reported experiments, which are confirmed through intercalation, modulates graphene The feasibility of electronic state.Have calculation shows that, in the graphene/carbon SiClx system after manganese intercalation, graphene and substrate Coupling is modulated by intercalation manganese atom.D-p hydridization occurs for intercalation manganese atom d electronics and graphene p electronics, makes in silicon carbide substrates Graphene restores its intrinsic Di Lake electronic state.The article being published in for 2016 on PHYSICAL REVIEW B magazine " Band-gap engineering by Bi intercalation of graphene on Ir (111) " is inserted by bismuth atom Layer, which is realized, makes the iridium substrate graphene of exposure (111) crystal face open the energy gap that a size is 420 milli electron-volts.Closely Phase, have calculation shows that, introducing magnetic intercalation can also be such that the Di Lake electronic state of graphene cleaves, opening energy gap.
Summary of the invention
The object of the present invention is to provide a kind of graphene/Mn5Ge3/ germanium (110) hetero-junctions and preparation method thereof, to solve Single crystal graphene does not have intrinsic energy gap in the prior art, therefore cannot be used to do semiconductor devices, and due to monocrystalline stone Coupling between black alkene and substrate can change the electric property of graphene, make what the actual performance of graphene had a greatly reduced quality to ask Topic.
In order to solve the above-mentioned technical problem, the invention adopts the following technical scheme:
According to the first aspect of the invention, a kind of graphene/Mn is provided5Ge3The preparation method of/germanium (110) hetero-junctions, packet Include following steps: S1: providing a kind of single-layer graphene sample, which includes germanium (110) substrate and at this The single-layer graphene grown on germanium (110) substrate, coverage rate of the single-layer graphene on germanium (110) substrate be 30%~ 70%；S2: the single-layer graphene sample being put into the sample preparation vacuum chamber with evaporation source and warm table and is heated, The vacuum degree of the sample preparation vacuum chamber is 5 × 10-10~1.5 × 10-9Millibar, the heating temperature of the single-layer graphene sample Degree is 1050~1150K, and the duration of heat is 20~30 hours；S3: change the heating temperature of the single-layer graphene sample For 600~650K, at the same using the evaporation source that source material is manganese metal on the single-layer graphene sample hydatogenesis metal Manganese；And S4: closing evaporation source, keeps heating temperature is constant to continue to heat sample, the duration of heat is 10~30 minutes, is taken Sample out obtains a kind of graphene/Mn5Ge3/ germanium (110) hetero-junctions.
According to a preferred embodiment of the invention, the single-layer graphene in the single-layer graphene sample of the step S1 Coverage rate on germanium (110) substrate is 50%~70%.
According to a preferred embodiment of the invention, the vacuum degree of sample preparation vacuum chamber described in the step S2 is 1.0×10-9~1.5 × 10-9The heating temperature of millibar, the single-layer graphene sample is 1100~1150K, when heating and continuous Between be 24~30 hours.
According to a preferred embodiment of the invention, the heated current of evaporation source is 3~7 amperes in the step S3, The emitting voltage of electron beam is 1.0~2.0 kilovolts, and the emission current of electron beam is 8~11 milliamperes, and evaporation time is 8~12 points Clock.
According to a preferred embodiment of the invention, the heated current of evaporation source is 5~7 amperes in the step S3, The emitting voltage of electron beam is 1.5~2.0 kilovolts, and the emission current of electron beam is 9~11 milliamperes, and evaporation time is 10~12 points Clock.
The single-layer graphene in the step S1 is grown on the germanium (110) substrate by chemical vapor deposition method On.
Germanium (110) substrate is germanium (110) monocrystalline that exposure is (110) crystal face.It should know, germanium single crystal is Germanium crystal without big angle crystal boundary or twin, in a kind of material of diamond lattice structure.And germanium (110) monocrystalline here is Refer to that exposure is the germanium crystal of (110) crystal face.
An optional embodiment according to the present invention, provides a kind of graphene/Mn5Ge3The preparation of/germanium (110) hetero-junctions Method includes the following steps S1: a kind of single-layer graphene sample is provided, the single-layer graphene sample include germanium (110) substrate with And the single-layer graphene grown on germanium (110) substrate, coverage rate of the single-layer graphene on germanium (110) substrate are 50%；S2: the single-layer graphene sample being put into the sample preparation vacuum chamber with evaporation source and warm table and is heated, The vacuum degree of the sample preparation vacuum chamber is 1.0 × 10-9Millibar, the heating temperature of the single-layer graphene sample are 1100K, The duration of heat is 24 hours；S3: the heating temperature of the single-layer graphene sample is changed into 625K, while using source material Material is the evaporation source of manganese metal on the single-layer graphene sample hydatogenesis manganese metal 10 minutes, and evaporation source heated current is 5 amperes, electron beam emitting voltage is 1.5 kilovolts, and electron beam emission current is 9 milliamperes；And S4: closing evaporation source, keeps adding Heat is temperature-resistant to be continued to heat sample, and the duration of heat is 10 minutes, takes out sample, obtains a kind of graphene/Mn5Ge3/ germanium (110) hetero-junctions.
According to the second aspect of the invention, a kind of graphene/Mn prepared according to above-mentioned preparation method is provided5Ge3/ germanium (110) hetero-junctions.
Graphene/the Mn5Ge3/ germanium (110) hetero-junctions includes: germanium (110) substrate；It is grown on germanium (110) substrate Single-layer graphene；And it is inserted into Mn of the germanium (110) between substrate and single-layer graphene5Ge3Alloy-layer.
The Mn5Ge3Alloy-layer is lath-shaped or plate, the Mn5Ge3The feature height of alloy-layer is at least 1.5nm.
It should be understood that obtained graphene/Mn produced according to the present invention5Ge3/ germanium (110) hetero-junctions is a kind of three-dimensional Structure, first layer are germanium single crystal substrate, second layer Mn5Ge3Alloy, top are graphene.It is of the present invention in germanium (110) The Mn grown on substrate graphene5Ge3Alloy-layer inserts between graphene and germanium (110) single crystalline substrate, the Mn5Ge3Alloy is main It introduces in step s3.
Mn of the present invention5Ge3The graphene of alloy intercalation surface covering has even curface, can directly carry out table Face atom level differentiates characterization and surface electronic state Spectroscopic Characterization, Mn5Ge3Alloy intercalation length is optionally, for example, 50~200nm.
Graphene/the Mn provided according to the present invention5Ge3/ germanium (110) hetero-junctions can be used for preparing graphene semiconductor device.
It should know, evaporation source, warm table and vacuum chamber are the conventional equipments of this field.
Should also it know, according to the present invention in provided preparation method, single-layer graphene involved in step S1 Sample belongs to a kind of material that those of ordinary skill in the art can obtain before this case applying date, and preparation method can refer to Document " how graphene islands are unidirectionally aligned on the Ge (110) surface, Jiayun Dai, Danxia Wang, et., Nano lett.2016,16,3160-3165 " and document " antibacterial ability and hemocompatibility of graphene functionalized germanium,Hao Geng, Jiayun Dai,et.,Scientific reports,2016”。
The working principle of the preparation method provided according to the present invention are as follows: on single-layer graphene sample of the evaporation source to heating When hydatogenesis manganese, manganese can form intermetallic compound Mn with germanium (110) substrate under single-layer graphene5Ge3, and formed Mn5Ge3Alloy is forming hetero-junctions between insertion single-layer graphene and germanium (110) substrate under the driving of planar growth.Graphene pair The manganese metal of hydatogenesis does not infiltrate so that graphene-structured completely retains, to obtain a kind of good heterojunction structure.
Inventive point of the invention essentially consists in: micrology characterization in tunnel is scanned as the hetero-junctions surface to obtained by, it can See that its alloy forms that significant etch features are obvious, and intercalation evidence is abundant, scanning tunneling microscopic composes result susceptible of proof and passes through Mn5Ge3 After magnetic alloy intercalation, graphene truly has the energy gap for opening 200 milli electron-volts, and the electricity for showing semi-conductor type materials is special Property.Meanwhile intercalation alloy surface is smooth, contacts with graphene well, realizes effectively modulation to the electronic state of graphene, makes intercalation Graphene opens the identical energy gap of size above alloy.These characteristics make graphene/Mn of the present invention5Ge3/ germanium (110) hetero-junctions can be applied to semiconductor field, because characteristic of semiconductor is presented in graphene electronic state, can be prepared into semiconductor device Part.
According to the present invention, a kind of graphene/Mn is provided5Ge3The preparation method of/germanium (110) hetero-junctions, this method utilize Molecular beam epitaxy (MBE) technology grows Mn using manganese metal as evaporation source source material5Ge3Alloy and in graphene and germanium (110) Between form intercalation configuration, prepare graphene/Mn5Ge3/ germanium (110) hetero-junctions, the preparation method have technical process simple, Controllability is good, and surface impurity is few, and be conducive to high-precision surface phenetic analysis the advantages that.According to the present invention, one kind is additionally provided Graphene/Mn5Ge3/ germanium (110) hetero-junctions, surface smoothness is high under vacuum for the hetero-junctions, can directly carry out surface atom grade Differentiate characterization and surface electronic state Spectroscopic Characterization.Tunnel micrology characterization is scanned as the hetero-junctions surface to obtained by, it is seen that Its alloy forms that significant etch features are obvious, and intercalation evidence is abundant, and scanning tunneling microscopic composes result susceptible of proof and passes through Mn5Ge3Magnetic Property alloy intercalation after, graphene truly have open 200 milli electron-volts energy gap, show the electrology characteristic of semi-conductor type materials. Meanwhile intercalation alloy surface is smooth, contacts with graphene well, realizes effectively modulation to the electronic state of graphene, closes intercalation Golden top graphene opens the identical energy gap of size.These characteristics make graphene/Mn of the present invention5Ge3/ germanium (110) Hetero-junctions can be applied to semiconductor field, because characteristic of semiconductor is presented in graphene electronic state, can be prepared into semiconductor devices.With Other are compared by the hetero-junctions that graphene intercalation method is formed, the intercalation material Mn of the structure5Ge3Alloy has ferromagnetism, this It lays a good foundation for research magnetism to the effect of graphene electronic state.
Detailed description of the invention
Fig. 1 is graphene/Mn described in embodiment 15Ge3The scanning tunneling microscopic figure of/germanium (110) hetero-junctions；
Fig. 2 is graphene/Mn described in embodiment 15Ge3The scanning tunneling microscopic of/germanium (110) hetero-junctions is composed；
Fig. 3 is the scanning tunneling microscopic figure of graphene/germanium (110) described in comparative example 1；
Fig. 4 is the scanning tunneling microscopic spectrum of graphene/germanium (110) described in comparative example 1；
Fig. 5 is graphene/amorphous state manganese/germanium (110) scanning tunneling microscopic figure described in comparative example 2；
Fig. 6 is graphene/manganese germanium alloy nano wire/germanium (110) scanning tunneling microscopic figure described in comparative example 3.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this The range of invention and is not intended to limit the present invention.
Embodiment 1
Germanium (110) substrate single-layer graphene of one piece of 50% coverage rate is put into the sample system with evaporation source and warm table In standby vacuum chamber, the vacuum degree of sample preparation vacuum chamber is 1 × 10-9Millibar.Degassing processing is carried out to it using warm table, is heated The emitting voltage of platform is 1000 volts, adjusts the heater current of warm table, so that its emission current is maintained at 9 milliamperes, heating 24 is small When.Whether the vacuum degree of sample preparation chamber can be deteriorated whithin a period of time in the process, can be used background vacuum to completing to remove Gas does auxiliary judgment.
Changing sample heating temperature after the completion of degasification is 625 Kelvins, opens the evaporation that evaporation source source material is manganese metal Source, the emitting voltage of electron beam are 1.5 kilovolts, adjust the heated current of evaporation source near 5 amperes (± 0.5 ampere), make electricity The emission current of beamlet is stablized at 9 milliamperes.It is kept for standing state 30 minutes, thermal station temperature to be added is constant, and evaporation source line is stablized Afterwards, adjustment warm table angle makes sample face evaporation source, opens evaporation source baffle, and using evaporation source, hydatogenesis is golden on sample Belong to manganese.After ten minutes, baffle is closed, evaporation source current is closed, adjusts warm table to horizontal position, the heating temperature of sample is not Become, heating after ten minutes, closes warm table, graphene/Mn5Ge3The preparation of/germanium (110) hetero-junctions is completed.
By gained graphene/Mn5Ge3It is aobvious that/germanium (110) hetero-junctions is put into the scanning-tunnelling in parallel with sample preparation vacuum chamber It is 5 × 10 in vacuum degree in micro mirror-11Millibar, temperature be 4.2 Kelvins under conditions of it is characterized.
Fig. 1 is the graphene/Mn prepared by the embodiment 15Ge3The scanning tunneling microscopic figure of/germanium (110) hetero-junctions, can See Mn5Ge3Alloy is inserted between graphene and germanium (110) substrate from graphene edge, there is mark when obvious formation alloy at step Will etching, and visible alloy insertion portion has apparent difference in surface roughness (within graphene domain with part is not inserted into The surface in region is cleaner).
Fig. 2 is graphene/Mn described in embodiment 15Ge3The scanning tunneling microscopic of/germanium (110) hetero-junctions is composed, can from spectrum Seeing has Mn5Ge3The graphene of alloy intercalation opens the energy gap that a size is 200 milli electron-volts.
Comparative example 1
Germanium (110) substrate single-layer graphene sample of one piece of 50% coverage rate is put into the sample with evaporation source and warm table Product are prepared in vacuum chamber, and the vacuum degree of sample preparation vacuum chamber is 1 × 10-9Millibar.Degassing processing is carried out to it using warm table, The emitting voltage of warm table is 1000 volts, adjusts the heater current of warm table, so that its emission current is maintained at 9 milliamperes, heating Stop heating after 24 hours, clean germanium (110) the substrate single-layer graphene sample in surface is made.
Fig. 3 is graphene/germanium scanning tunneling microscopic figure described in comparative example 1, it is seen that is not had at graphene domain edge The sign that intercalation occurs, graphene inside and not formed three layers of heterojunction structure.Fig. 4 is graphene/germanium described in comparative example 1 (110) scanning tunneling microscopic spectrum, it is seen that graphene is in no Mn5Ge3There is no intrinsic semiconductor energy gaps when alloy intercalation.
According to the comparison of above-described embodiment 1 and comparative example 1 it is found that the heterojunction structure obtained after growth course is really people For the Mn of introducing5Ge3Alloy Heterojunction structure.It, will not under identical thermodynamic condition if not introducing manganese element (comparative example 1) Grow graphene/manganese germanium alloy/germanium (110) heterojunction structure.
Comparative example 2
Germanium (110) substrate single-layer graphene of one piece of 50% coverage rate is put into the sample system with evaporation source and warm table In standby vacuum chamber, the vacuum degree of sample preparation vacuum chamber is 1 × 10-9Millibar.Degassing processing is carried out to it using warm table, is heated The emitting voltage of platform is 1000 volts, adjusts the heater current of warm table, so that its emission current is maintained at 9 milliamperes, heating 24 is small When.Whether the vacuum degree of sample preparation chamber can be deteriorated whithin a period of time in the process, can be used background vacuum to completing to remove Gas does auxiliary judgment.
Warm table is closed after the completion of degasification, opens the evaporation source that evaporation source source material is manganese metal, the transmitting electricity of electron beam Pressure is 1.5 kilovolts, adjusts the heated current of evaporation source near 5 amperes (± 0.5 ampere), stablizes the emission current of electron beam At 9 milliamperes.It is kept for standing state 30 minutes, sample to be added is cooled to room temperature, and after evaporation source line is stablized, adjusts warm table angle Make sample face evaporation source, open evaporation source baffle, using evaporation source on sample hydatogenesis manganese metal.After ten minutes, it closes Baffle is closed, evaporation source current is closed, adjustment warm table to horizontal position heats sample, and heating temperature is 625 Kelvins, heating After ten minutes, warm table is closed, graphene/amorphous state manganese/germanium (110) hetero-junctions preparation is completed.
Gained graphene/amorphous state manganese/germanium (110) hetero-junctions is put into the scanning tunnel in parallel with sample preparation vacuum chamber It is 5 × 10 in vacuum degree in road microscope-11Millibar, temperature be 4.2 Kelvins under conditions of it is characterized.
Fig. 5 is graphene/amorphous state manganese/germanium (110) hetero-junctions scanning tunneling microscopic prepared by the comparative example 2 Figure, there is no the Mn of lath-shaped for discovery5Ge3Alloy intercalation configuration is formed.Therefore, evaporation source deposited metal on substrate is being used Carrying out heating to substrate while manganese is to form graphene/Mn5Ge3The committed step of/germanium (110) hetero-junctions.
Comparative example 3
Germanium (110) substrate single-layer graphene of one piece of 100% coverage rate is put into the sample with evaporation source and warm table It prepares in vacuum chamber, the vacuum degree of sample preparation vacuum chamber is 1 × 10-9Millibar.Degassing processing is carried out to it using warm table, is added The emitting voltage of thermal station is 1000 volts, adjusts the heater current of warm table, so that its emission current is maintained at 9 milliamperes, heating 24 Hour.Whether the vacuum degree of sample preparation chamber can be deteriorated whithin a period of time in the process, can be used background vacuum to completing Auxiliary judgment is done in degasification.
Changing sample heating temperature after the completion of degasification is 625 Kelvins, opens the evaporation that evaporation source source material is manganese metal Source, the emitting voltage of electron beam are 1.5 kilovolts, adjust the heated current of evaporation source near 5 amperes (± 0.5 ampere), make electricity The emission current of beamlet is stablized at 9 milliamperes.It is kept for standing state 30 minutes, thermal station temperature to be added is constant, and evaporation source line is stablized Afterwards, adjustment warm table angle makes sample face evaporation source, opens evaporation source baffle, and using evaporation source, hydatogenesis is golden on sample Belong to manganese.After ten minutes, baffle is closed, evaporation source current is closed, adjusts warm table to horizontal position, the heating temperature of sample is not Become, heating after ten minutes, closes warm table, and graphene/manganese germanium alloy nano wire/germanium (110) hetero-junctions preparation is completed.
Gained graphene/manganese germanium alloy nano wire/germanium (110) hetero-junctions is put into parallel with sample preparation vacuum chamber sweep It retouches in tunnel microscope, is 5 × 10 in vacuum degree-11Millibar, temperature be 4.2 Kelvins under conditions of it is characterized.
Fig. 6 is graphene/manganese germanium alloy nano wire/germanium (110) hetero-junctions scanning-tunnelling prepared by the comparative example 3 Micrograph, it is seen that manganese is inserted between graphene and germanium (110) substrate from the step of germanium substrate, forms graphene/manganese germanium alloy Nano wire/germanium (110) hetero-junctions, and not formed graphene/Mn5Ge3/ germanium (110) hetero-junctions.Therefore, it is covered using 30%~70% Germanium (110) substrate single-layer graphene of lid rate is to form graphene/Mn5Ge3The committed step of/germanium (110) hetero-junctions.
Above-described, only presently preferred embodiments of the present invention, the range being not intended to limit the invention, of the invention is upper Stating embodiment can also make a variety of changes.Letter made by all claims applied according to the present invention and description Single, equivalent changes and modifications, fall within the claims of the invention patent.The not detailed description of the present invention is normal Advise technology contents.

Claims (10)

1. a kind of graphene/Mn5Ge3The preparation method of/germanium (110) hetero-junctions, which comprises the following steps:
S1: providing a kind of single-layer graphene sample, which includes germanium (110) substrate and in the germanium (110) The single-layer graphene grown on substrate, coverage rate of the single-layer graphene on germanium (110) substrate are 30%~70%；
S2: the single-layer graphene sample being put into the sample preparation vacuum chamber with evaporation source and warm table and is heated, The vacuum degree of the sample preparation vacuum chamber is 5 × 10-10~1.5 × 10-9Millibar, the heating temperature of the single-layer graphene sample Degree is 1050~1150K, and the duration of heat is 20~30 hours；
S3: the heating temperature of the single-layer graphene sample is changed into 600~650K, while the use of source material being manganese metal Evaporation source hydatogenesis manganese metal on the single-layer graphene sample；And
S4: closing evaporation source, keeps the constant continuation heating stepses S3 products therefrom of heating temperature, and the duration of heat is 10~30 Minute, it takes out, obtains a kind of graphene/Mn5Ge3/ germanium (110) hetero-junctions.
2. preparation method according to claim 1, which is characterized in that in the step S1, in single-layer graphene sample Coverage rate of the single-layer graphene on germanium (110) substrate is 50%~70%.
3. preparation method according to claim 1, which is characterized in that in the step S2, the sample preparation vacuum chamber Vacuum degree be 1.0 × 10-9~1.5 × 10-9Millibar, the heating temperature of the single-layer graphene sample are 1100~1150K, The duration of heat is 24~30 hours.
4. preparation method according to claim 1, which is characterized in that in the step S3, the heated current of evaporation source is 3 ~7 amperes, the emitting voltage of electron beam is 1.0~2.0 kilovolts, and the emission current of electron beam is 8~11 milliamperes, and evaporation time is 8~12 minutes.
5. the preparation method according to claim 4, which is characterized in that in the step S3, the heated current of evaporation source is 5 ~7 amperes, the emitting voltage of electron beam is 1.5~2.0 kilovolts, and the emission current of electron beam is 9~11 milliamperes, and evaporation time is 10~12 minutes.
6. preparation method according to claim 1, which is characterized in that in the step S1, the single-layer graphene is logical Chemical vapor deposition method is crossed to be grown on the germanium (110) substrate that the single-layer graphene sample is made.
7. preparation method according to claim 1, which is characterized in that germanium (110) substrate is that exposure is that (110) are brilliant Germanium (110) monocrystalline in face.
8. a kind of graphene/Mn that preparation method according to any one of claims 1-7 is prepared5Ge3/ germanium (110) hetero-junctions.
9. graphene/Mn according to claim 85Ge3/ germanium (110) hetero-junctions, which is characterized in that the graphene/ Mn5Ge3/ germanium (110) hetero-junctions includes:
Germanium (110) substrate；
The single-layer graphene grown on germanium (110) substrate；And
It is inserted into Mn of the germanium (110) between substrate and single-layer graphene5Ge3Alloy-layer.
10. graphene/Mn according to claim 95Ge3/ germanium (110) hetero-junctions, which is characterized in that the Mn5Ge3Alloy Layer is lath-shaped or plate, and feature height is at least 1.5nm.
CN201910329382.5A 2019-04-23 2019-04-23 graphene/Mn5Ge3Germanium (110) heterojunction and method for producing the same Expired - Fee Related CN110004488B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910329382.5A CN110004488B (en) 2019-04-23 2019-04-23 graphene/Mn5Ge3Germanium (110) heterojunction and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910329382.5A CN110004488B (en) 2019-04-23 2019-04-23 graphene/Mn5Ge3Germanium (110) heterojunction and method for producing the same

Publications (2)

Publication Number Publication Date
CN110004488A true CN110004488A (en) 2019-07-12
CN110004488B CN110004488B (en) 2020-04-03

Family

ID=67173675

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910329382.5A Expired - Fee Related CN110004488B (en) 2019-04-23 2019-04-23 graphene/Mn5Ge3Germanium (110) heterojunction and method for producing the same

Country Status (1)

Country Link
CN (1) CN110004488B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105597669A (en) * 2015-10-15 2016-05-25 南昌航空大学 Preparation method and application of core-shell structured graphene/Mn3O4 nanocomposite material
US9396935B1 (en) * 2015-05-19 2016-07-19 Samsung Electronics Co., Ltd. Method of fabricating ultra-thin inorganic semiconductor film and method of fabricating three-dimensional semiconductor device using the same
CN108751181A (en) * 2018-07-03 2018-11-06 清华大学 Heterojunction structure porous oxidation graphene film preparation method, graphene film and generator

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9396935B1 (en) * 2015-05-19 2016-07-19 Samsung Electronics Co., Ltd. Method of fabricating ultra-thin inorganic semiconductor film and method of fabricating three-dimensional semiconductor device using the same
CN105597669A (en) * 2015-10-15 2016-05-25 南昌航空大学 Preparation method and application of core-shell structured graphene/Mn3O4 nanocomposite material
CN108751181A (en) * 2018-07-03 2018-11-06 清华大学 Heterojunction structure porous oxidation graphene film preparation method, graphene film and generator

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUANCHANG LI ET AL.: "Dirac Fermions in Strongly Bound Graphene Systems", 《PHYSICAL REVIEW LETTERS》 *

Also Published As

Publication number Publication date
CN110004488B (en) 2020-04-03

Similar Documents

Publication Publication Date Title
Wasa et al. Thin film materials technology: sputtering of control compound materials
Li et al. ZnO nanobelts grown on Si substrate
Li et al. Preparation of network-like MgO nanobelts on Si substrate
Roth et al. Silicon epitaxy by solid‐phase crystallization of deposited amorphous films
CN108193276B (en) Method for preparing large-area single-orientation hexagonal boron nitride two-dimensional atomic crystal
KR102109347B1 (en) Preparing method of doped metal-chalcogenide thin film
CN109205599B (en) Method for preparing graphene single crystal wafer at low temperature
US20030126742A1 (en) Method of fabrication of ZnO nanowires
CN100545314C (en) Be used to prepare the in-situ treatment method of sapphire substrate of high-quality zinc oxide film
Bajor et al. Growth of high quality epitaxial Ge films on (100) Si by sputter deposition
Sasase et al. Formation of ‘environmentally friendly’semiconductor (β-FeSi2) thin films prepared by ion beam sputter deposition (IBSD) method
JP2020531682A (en) Single-layer and multi-layer silicene prepared by plasma chemical vapor deposition
CN110004488A (en) A kind of graphene/Mn5Ge3/ germanium (110) hetero-junctions and preparation method thereof
CN114477105B (en) Two-dimensional BiCuSeO nanosheet, preparation method thereof and semiconductor device
US5326424A (en) Cubic boron nitride phosphide films
CN110697696B (en) Method for preparing single-layer graphene in large area by utilizing metal intercalation
Vouroutzis et al. Growth of β-FeSi2 particles on silicon by reactive deposition epitaxy
Xiao et al. Annealing effects on the formation of semiconducting Mg2Si film using magnetron sputtering deposition
Cai et al. Fabrication of well-aligned Er nanowires on vicinal silicon (001) surfaces
CN112689609A (en) Black phosphorus phase ultrathin bismuth nanosheet modified composite film and preparation method thereof
Lin et al. Synthesis and Properties of 2D Semiconductors
JP3916454B2 (en) Method for producing β-FeSi2 thin film
WO2023168356A2 (en) Hybrid covalent-van der waals system 2d heterostructures by dative epitaxy
JP4854180B2 (en) Method for producing InSb nanowire structure
JP2814503B2 (en) Method for producing single crystal diamond film composite

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20200403

CF01 Termination of patent right due to non-payment of annual fee